CN104855416A - High-temperature-resistant composite antibacterial agent and preparation method thereof - Google Patents

High-temperature-resistant composite antibacterial agent and preparation method thereof Download PDF

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CN104855416A
CN104855416A CN201510274686.8A CN201510274686A CN104855416A CN 104855416 A CN104855416 A CN 104855416A CN 201510274686 A CN201510274686 A CN 201510274686A CN 104855416 A CN104855416 A CN 104855416A
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antibacterial agent
polytrimethylene
guanidine
poly
hexamethylene biguanide
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CN104855416B (en
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李健雄
唐启明
汪川
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Jie Sheng Bio Tech Ltd Wuhan
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Jie Sheng Bio Tech Ltd Wuhan
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Abstract

The invention discloses a high-temperature-resistant composite antibacterial agent and a preparation method thereof, and belongs to the technical field of bactericides. The composite antibacterial agent comprises a guanidine salt antibacterial agent and inorganic additives, wherein the inorganic additives are selected from one or more of boric acid, boric oxide, zinc oxide, titanium dioxide, phosphoric acid, zeolite powder, silica gel powder, glass powder, talcum powder and hydroxyapatite. The preparation method comprises the following steps: adding a small number of volatile solvents into the guanidine salt antibacterial agent and the inorganic additives, mixing to be pasty, and uniformly grinding to obtain the high-temperature-resistant composite antibacterial agent; or dissolving the guanidine salt antibacterial agent and the inorganic additives into the solvents, and steaming and removing the solvents to obtain the high-temperature-resistant composite antibacterial agent. The composite antibacterial agent can integrate the immediate action, the broad spectrum and the continuity of an organic system with the safety and the heat resistance of an inorganic system. Compared with an undoped antibacterial agent, the high-temperature-resistant composite antibacterial agent has the advantage that the heat stability is obviously improved. Other accessory components can be added into the antibacterial agent according to specific application.

Description

A kind of high temperature resistant complex antimicrobials and preparation method thereof
Technical field
The present invention relates to bactericide technical field, be specifically related to a kind of high temperature resistant complex antimicrobials and preparation method thereof.
Background technology
Anti-biotic material is that a class possesses antibacterial and new material that is sterilizing function, and obtain by adding one or more specific antibacterial agents, from the development of domestic and international anti-biotic material, antibiotic plastic is with fastest developing speed, most widely used anti-biotic material.
Antibacterial agent is of a great variety, be broadly divided into inorganic according to its chemical composition, organic and natural three major types, inorganic antiseptic present stage is most widely used general in antibiotic plastic, the antibacterial agent that market is maximum, main based on silver-series antibacterial agent, be characterized in that safety warm tolerance durability is better, use more antibacterial agent in current compo, weak point is the late effect property that price is higher and antibacterial, bacterium can not can be killed rapidly as organic antibacterial agent, and to fungi, mould does not almost have inhibition, the chemical property of silver is active simultaneously, the oxidizable silver oxide forming dark color, thus reduce antibacterial efficacy and affect products appearance, in addition, inorganic antibiosis powder and polymer-polymer miscibility poor, be easy to reunite in matrix plastic, very large difficulty can be brought to processing such as the spinning membranes of material.Compared with inorganic antibacterial, its antibacterial speed of organic antibacterial agent is faster than inorganic antiseptic, anti-mold effect is good, the process operability added in the plastic is better than inorganic antiseptic, in storage and use procedure, colour stability is also strong than inorganic antiseptic, and thus organic antibacterial agent is more and more extensive in the application of plastics.
Guanidine salt polymer (poly-guanidine) is a kind of polymer based on guanidino group, be the nineties occur a kind of wide spectrum, efficient, nontoxic, non-stimulated, to human temperature and harmless new type bactericide, the sterilizing in the field such as weaving, agricultural, food, hospital, plastics, rubber, fiber can be widely used in, become the study hotspot in sterilization field in recent years.Current existing guanidine salt polymer kind comprises other inorganic acid salt and the organic acid salt, polyoxyethylene groups guanidine etc. of polyhexamethylene (two) guanidine hydrochloride, polyhexamethylene (two) guanidine propionate, polyhexamethylene (two) guanidine stearate or polyhexamethylene (two) guanidine, and among many new guanidine salt polymers are being developed.
Patent CN101037503A, disclose a kind of production method preparing polyhexamethylene guanide propionate powder, this invention utilizes ion isolation exchange membrane, successfully polyhexamethylene guanide propionate is separated from the aqueous solution, make powdered samples, overcome the strong hygroscopic shortcoming of poly-guanidine propionate, make it may be used for the Antibacterial accessory ingredient of plastics, fiber and rubber.
Document Synthesis and antimicrobial activityof polymeric guanidine andbiguanidine salts, Polymer 40 (1999) 6189-6198 reports polyhexamethylene (two) guanidine stearate at the temperature of 280 DEG C, to various bacteria and fungi, still there is good bactericidal effect, therefore may be used for the antimicrobial treatment of the polymer such as polypropylene, nylon.But experiment finds that its antibiotic property of poly hexamethylene biguanide stearate of hydrophobe is far short of what is expected relative to water miscible hydrochloride propionate, in addition, poly hexamethylene biguanide stearate joins after in plastics, easily make goods yellowish, limit its white or clear plastic articles in application.
Patent CN1350022A, CN1445270A, CN1569923A, US728253882 discloses a kind of method preparing the polymer of polyamine and guanidine salt polymer, this guanidine salt polymer product there is the active group that can carry out grafting, comprise double bond, epoxide group etc., then fusion method is utilized, this guanidine salt polymer and resin are made antibacterial matrices according to higher ratio by solwution method or solid phase method, then master batch is utilized to prepare corresponding antibiotic plastic, these utilize guanidine salt polymer to prepare antibiotic plastic needs and are first prepared into antibacterial matrices, step is more loaded down with trivial details, cause cost higher, and the color of antibacterial matrices product is more yellow, certain influence is had to the color of end article
Therefore, develop a kind of germicidal efficiency high, high temperature resistant, do not affect goods color, preparation method is simple, and the biguanides antibacterial agent that can directly add in resin has important scientific research and practical value.
Summary of the invention
In order to solve the problem, embodiments provide a kind of high temperature resistant complex antimicrobials and preparation method thereof, this antibacterial agent can take into account the prompt effect of organic system, broad spectrum activity, the safety of continuation and inorganic system, warm tolerance.Described scheme is as follows:
On the one hand, embodiments provide a kind of high temperature resistant complex antimicrobials, comprise guanidinesalt antibacterial agent and inorganic additive.Wherein, the mass content of inorganic additive is 1-99%; Wherein, inorganic additive is selected from one or more in boric acid, boron oxide, zinc oxide, titanium dioxide, phosphoric acid, zeolite powder, silica white, glass dust, talcum powder and hydroxyapatite etc.; Wherein, guanidine salt polymer is selected from single guanidine, biguanides and composition thereof.Wherein, inorganic additive has good heat resistance, is combined with aforementioned organic antibacterial agent, the synergy both playing.Such as boric acid has originally been born with antibacterial activity, and the product after being combined with guanidine bactericides not only has good heat resistance, can reduce the loss of this life of boric acid simultaneously, increase its antibacterial action.In addition, this complex antimicrobials can also add other functional mass, as oxidant.
Wherein, the guanidinesalt antibacterial agent in the embodiment of the present invention is selected from poly (hexamethylene) hydrochloride, polyhexamethylene guanidine carbonate, polyhexamethylene guanidine nitrate, polyhexamethylene guanide phosphate, polyhexamethylene guanidine sulfate, polyhexamethylene guanide acetate, polyhexamethylene guanide propionate, polyhexamethylene guanide lauric acid, polyhexamethylene guanide stearate, polyhexamethylene guanide sulfonate, polyhexamethylene guanide pyrithione hydrochlorate, polyhexamethylene guanide sorbate, polyhexamethylene guanide benzoate, polyhexamethylene guanide P-hydroxybenzoic acid, polytrimethylene guanidine hydrochloride, polytrimethylene guanidine propionate, polytrimethylene guanidine lauric acid, polytrimethylene guanidine stearate, polytrimethylene guanidine pyrithione hydrochlorate, polytrimethylene guanidine sorbate, polytrimethylene guanidine benzoate, polytrimethylene guanidine P-hydroxybenzoic acid, hexamethylene, poly hexamethylene biguanide carbonate, poly hexamethylene biguanide nitrate, poly hexamethylene biguanide phosphate, poly hexamethylene biguanide sulphate, poly hexamethylene biguanide acetate, poly hexamethylene biguanide propionate, poly hexamethylene biguanide lauric acid, poly hexamethylene biguanide stearate, poly hexamethylene biguanide sulfonate, poly hexamethylene biguanide pyrithione hydrochlorate, poly hexamethylene biguanide sorbate, poly hexamethylene biguanide benzoate, poly hexamethylene biguanide P-hydroxybenzoic acid, polytrimethylene biguanide hydrochloride, polytrimethylene biguanides propionate, polytrimethylene biguanides lauric acid, polytrimethylene biguanides stearate, polytrimethylene biguanides pyrithione hydrochlorate, polytrimethylene biguanides sorbate, polytrimethylene biguanides benzoate, polytrimethylene biguanides P-hydroxybenzoic acid, chlorohexidene, chlorhexidine hydrochloride, chlorhexidine acetate, one or more in phosphoric acid chlorohexidene and boric acid chlorohexidene etc.
Preferably, the inorganic additive in the embodiment of the present invention is selected from boric acid, boron oxide and composition thereof.
Preferably, the mass content of the inorganic additive in the embodiment of the present invention is 5%-90%; More preferably, the mass content of the inorganic additive in the embodiment of the present invention is 5%-50%.
Preferably, the guanidinesalt antibacterial agent in the embodiment of the present invention is selected from poly (hexamethylene), cosmocil stearate and composition thereof, and inorganic additive is selected from boric acid, boron oxide and composition thereof.
On the other hand, the embodiment of the present invention additionally provides the preparation method of aforementioned high temperature resistant complex antimicrobials, and it specifically can adopt the following two kinds method to prepare:
Method one, in guanidinesalt antibacterial agent and inorganic additive, add a small amount of solvent flashing furnishing pasty state, grind even after obtain complex antimicrobials.
Method two, guanidinesalt antibacterial agent and inorganic additive to be dissolved in solvent, then to be steamed by solvent and remove and obtain warm complex antimicrobials, wherein, solvent comprises the alcohol etc. of water or solubilized guanidinesalt antibacterial agent, as methyl alcohol, ethanol or propyl alcohol.
Particularly, in chlorohexidene and titanium dioxide, add a small amount of solvent flashing furnishing pasty state, after fully mixing with ball mill, namely obtain complex antimicrobials.By poly (hexamethylene) hydrochloride, hexamethylene or both mixtures and boric acid soluble in water, then water steamed namely obtain complex antimicrobials except rear.
Meanwhile, this antibacterial agent also can an embody rule and add other and assist a ruler in governing a country composition, as stabilizing agent or antioxidant.Heat stabilizer is one of important class in plastic processing additives, with the birth of polyvinyl chloride resin with develop synchronous, is also mainly used in polyvinyl chloride resin processing.Some material also can add other additive, as fire retardant.Antioxidant (Antioxidants) stops the dysgenic material of oxidation, and it is that a class can help to catch also and free radical, thus dispels a class material of free radical damage.The application of antioxidant is very extensive, all can use in many materials.These additives can comprise following material: 2, 6-di-tert-butyl-4-methy phenol (264), four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (1076), 2, 2 ' monothio two [3 one (3, 5. di-t-butyl .4. hydroxy phenyl) ethyl propionate (SKY-1035), tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester (PKY-168), two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites (JC-242) etc. and compound thereof.
This complex antimicrobials comprises organic antibacterial agent/inorganic adsorbent dispersion, organic antibacterial agent generally chooses single guanidine, biguanides, inorganic system generally chooses the inorganic particulate itself with sterilization and anticorrosion, the prompt effect of organic system can be taken into account, broad spectrum activity, the safety of continuation and inorganic system, warm tolerance, be there is by some of mixing 1-99% the inorganic particulate of special nature, compared with unadulterated antibacterial agent, its heat endurance is all improved significantly, antibacterial agent as composite in hexamethylene/boric acid/both systems, its high temperature resistance color changeable effect is good, 295 DEG C of non-yellowing nondiscolourings.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below embodiment of the present invention is described further in detail.
Organic single guanidine or biguanides and inorganic matter additive are weighed up with the ratio of suitable weight ratio, and be dissolved or dispersed in polarity alcohol (as methyl alcohol, ethanol) or water, solvent evaporated obtains homogeneity powder, also directly can mix without solvent.Gained compound product is put into 120-350 DEG C of Muffle furnace and is heated, and slowly heats up, and observes color change; As a comparison, generally the organic antibacterial agent of the inorganic particulate that do not adulterate is put into Muffle furnace simultaneously, slowly heat up, observe the change of its color.Below in conjunction with instantiation, the present invention will be further described, but the present invention is not limited to following embodiment
Example 1:
Take hexamethylene 50 grams and be dissolved in 200 grams of water, and take boric acid 2.6 grams (volume 5%) in addition and be dissolved in 30 grams of water, both are uniformly mixed, after evaporate to dryness water colourless powder, be placed in Muffle furnace heating 15 minutes; Compare with pure hexamethylene simultaneously.
Example 2:
Take hexamethylene 50 grams and be dissolved in 200 grams of water, and take boric acid 5.6 grams (volume 10%) in addition and be dissolved in 30 grams of water, both are uniformly mixed, after evaporate to dryness water colourless powder, be placed in Muffle furnace heating 15 minutes; Compare with pure hexamethylene simultaneously.
Example 3:
Take hexamethylene 50 grams and be dissolved in 200 grams of water, and take boric acid 8.8 grams (volume 15%) in addition and be dissolved in 30 grams of water, both are uniformly mixed, after evaporate to dryness water colourless powder, be placed in Muffle furnace heating 15 minutes; Compare with pure hexamethylene simultaneously.
Example 4:
Take hexamethylene 50 grams, take boric acid 11.5 grams (volume 15%) in addition, titanium dioxide 15.4 grams (volume 20%), mixes three in ball mill, is placed in Muffle furnace heating 15 minutes; Compare with pure hexamethylene simultaneously.
Example 5:
Take poly hexamethylene biguanide propionate 50 grams and be dissolved in 200 grams of water, and claim in addition boric acid 8.8(volume 15%) gram be dissolved in 30 grams of water, both are uniformly mixed, after evaporate to dryness water colourless powder, be placed in Muffle furnace heating 15 minutes; Compare with pure hexamethylene simultaneously.
Example 6:
Take poly (hexamethylene) hydrochloride 50 grams and be dissolved in 150 grams of water, and claim boric acid 8.8 grams to be dissolved in 30 grams of water in addition, both are uniformly mixed, after evaporate to dryness water, obtain colourless powder, be placed in Muffle furnace heating 15 minutes; Compare with pure poly (hexamethylene) hydrochloride simultaneously.
Example 7:
Take chlorhexidine hydrochloride 10 grams, titanium dioxide 40 grams (volume 80%), add about 10 grams of isopropyl alcohol furnishing pasty states, grind in mortar and after isopropyl alcohol volatilizees completely, obtain homodisperse white powder in 1 hour, be placed in Muffle furnace heating 15 minutes; Compare with pure hydrochloric acid chlorohexidene simultaneously.
Example 8:
Take phosphoric acid chlorohexidene 10 grams, mix titanium dioxide 10 grams, after using grinder to mix, obtain homodisperse white powder, be placed in Muffle furnace heating 15 minutes; Compare with pure phosphoric acid chlorohexidene simultaneously.
Example 9:
Take boric acid chlorohexidene 10 grams, mix boric acid 10 grams and titanium dioxide 40 grams respectively, after using grinder to mix, obtain homodisperse white powder, be placed in Muffle furnace heating 15 minutes; Compare with pure boric acid chlorohexidene simultaneously.
Table 1 is the warm tolerance result of different system:
Table 1
Guanidinesalt antibacterial agent Inorganic doping thing Inorganics doped amount (%) The highest discoloring temperature
Hexamethylene Do not mix 0 250
Hexamethylene Silica 10 270
Hexamethylene Boric acid 5 270
Hexamethylene Boric acid 10 280
Hexamethylene Boric acid 15 295
Hexamethylene Boric acid+titanium dioxide 15+20 310
Hexamethylene Diboron trioxide 15 280
Hexamethylene Titanium dioxide 10 270
Hexamethylene Silica 10 260
Poly hexamethylene biguanide propionate Do not mix 0 250
Poly hexamethylene biguanide propionate Boric acid 15 260
Poly (hexamethylene) hydrochloride Do not mix 0 280
Poly (hexamethylene) hydrochloride Boric acid 10 300
Poly (hexamethylene) hydrochloride Boric acid 15 320
Poly (hexamethylene) hydrochloride Boric acid 20 305
Poly (hexamethylene) hydrochloride Diboron trioxide 25 300
Chlorohexidene alkali Do not mix 0 135
Chlorohexidene alkali Boric acid 20 240
Chlorohexidene alkali Boric acid+titanium dioxide 20+50 270
Chlorhexidine hydrochloride Do not mix 0 250
Chlorhexidine hydrochloride Titanium dioxide 80 290
Phosphoric acid chlorohexidene Do not mix 0 210
Phosphoric acid chlorohexidene Titanium dioxide 50 250
Boric acid chlorohexidene Do not mix 0 220
Boric acid chlorohexidene Titanium dioxide 50 260
Boric acid chlorohexidene Titanium dioxide 80 280
In a word, by mixing the inorganic particulate with specific function of 1-99%, compared with unadulterated antibacterial agent, its heat-resistant stability all obtains raising to a certain extent, and the method technique is simple, and operability is good, significant for the resistant to elevated temperatures plastic products of exploitation.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (9)

1. a high temperature resistant complex antimicrobials, it is characterized in that, comprise guanidinesalt antibacterial agent and inorganic additive, the mass content of described inorganic additive is 1-99%, described inorganic additive be selected from boric acid, boron oxide, zinc oxide, titanium dioxide, phosphoric acid, zeolite powder, silica white, glass dust, talcum powder and hydroxyapatite one or more, described guanidinesalt antibacterial agent is selected from single guanidine, biguanides and composition thereof.
2. high temperature resistant complex antimicrobials according to claim 1, is characterized in that, described guanidinesalt antibacterial agent is selected from poly (hexamethylene) hydrochloride, polyhexamethylene guanidine carbonate, polyhexamethylene guanidine nitrate, polyhexamethylene guanide phosphate, polyhexamethylene guanidine sulfate, polyhexamethylene guanide acetate, polyhexamethylene guanide propionate, polyhexamethylene guanide lauric acid, polyhexamethylene guanide stearate, polyhexamethylene guanide sulfonate, polyhexamethylene guanide pyrithione hydrochlorate, polyhexamethylene guanide sorbate, polyhexamethylene guanide benzoate, polyhexamethylene guanide P-hydroxybenzoic acid, polytrimethylene guanidine hydrochloride, polytrimethylene guanidine propionate, polytrimethylene guanidine lauric acid, polytrimethylene guanidine stearate, polytrimethylene guanidine pyrithione hydrochlorate, polytrimethylene guanidine sorbate, polytrimethylene guanidine benzoate, polytrimethylene guanidine P-hydroxybenzoic acid, hexamethylene, poly hexamethylene biguanide carbonate, poly hexamethylene biguanide nitrate, poly hexamethylene biguanide phosphate, poly hexamethylene biguanide sulphate, poly hexamethylene biguanide acetate, poly hexamethylene biguanide propionate, poly hexamethylene biguanide lauric acid, poly hexamethylene biguanide stearate, poly hexamethylene biguanide sulfonate, poly hexamethylene biguanide pyrithione hydrochlorate, poly hexamethylene biguanide sorbate, poly hexamethylene biguanide benzoate, poly hexamethylene biguanide P-hydroxybenzoic acid, polytrimethylene biguanide hydrochloride, polytrimethylene biguanides propionate, polytrimethylene biguanides lauric acid, polytrimethylene biguanides stearate, polytrimethylene biguanides pyrithione hydrochlorate, polytrimethylene biguanides sorbate, polytrimethylene biguanides benzoate, polytrimethylene biguanides P-hydroxybenzoic acid, chlorohexidene, chlorhexidine hydrochloride, chlorhexidine acetate, one or more in phosphoric acid chlorohexidene and boric acid chlorohexidene.
3. high temperature resistant complex antimicrobials according to claim 1, is characterized in that, described inorganic additive is selected from boric acid, boron oxide and composition thereof.
4. high temperature resistant complex antimicrobials according to claim 1 and 2, is characterized in that, the mass content of described inorganic additive is 5%-50%.
5. high temperature resistant complex antimicrobials according to claim 1, is characterized in that, described guanidinesalt antibacterial agent is selected from poly (hexamethylene), cosmocil stearate and composition thereof, and described inorganic additive is selected from boric acid, boron oxide and composition thereof.
6. the preparation method of the high temperature resistant complex antimicrobials as described in any one of claim 1-5, is characterized in that, adds a small amount of solvent flashing furnishing pasty state in guanidinesalt antibacterial agent and inorganic additive, grinds evenly to obtain high temperature resistant complex antimicrobials; Or, guanidinesalt antibacterial agent and inorganic additive are dissolved in solvent, then solvent steaming are removed to obtain high temperature resistant complex antimicrobials.
7. preparation method according to claim 6, is characterized in that, described solvent comprises the alcohol of water or solubilized guanidinesalt antibacterial agent.
8. preparation method according to claim 6, is characterized in that, adds a small amount of solvent flashing furnishing pasty state, obtain complex antimicrobials after fully mixing with ball mill in chlorohexidene and titanium dioxide.
9. preparation method according to claim 6, is characterized in that, by poly (hexamethylene) hydrochloride, hexamethylene or both mixtures and boric acid soluble in water, then by water steam remove to obtain complex antimicrobials.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105568676A (en) * 2015-12-22 2016-05-11 常熟市泽众家用纺织品有限公司 Pillowcase fabric
CN106674754A (en) * 2016-12-29 2017-05-17 上海普利特复合材料股份有限公司 Halogen-free flame-retardant high-heat-resistance antibacterial polypropylene composite material and preparation method thereof
CN107099031A (en) * 2017-04-21 2017-08-29 石家庄学院 A kind of heat resist modification polyhexamethylene guanide and its production and use
CN108048169A (en) * 2017-12-18 2018-05-18 徐润宝 A kind of wear-resistant antioxygen engine lubricating oil
CN108486680A (en) * 2018-01-30 2018-09-04 宁波三邦超细纤维有限公司 Compound imitative ice silk fiber of colored polyester-nylon and preparation method thereof
CN109295572A (en) * 2018-10-16 2019-02-01 宜城市天舒纺织有限公司 A kind of antibacterial Quality Pure Cotton Yarn Production production technology
CN109303050A (en) * 2018-07-26 2019-02-05 合肥华盖生物科技有限公司 A kind of high temperature resistant type complex antimicrobials and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1350022A (en) * 2000-10-19 2002-05-22 上海塑杰科技有限公司 Polyamine-guanidine salt polymer and its prepn
CN1445270A (en) * 2002-03-15 2003-10-01 上海塑杰科技有限公司 Functional agglomerates of polyolefin as well as its preparing method and application
CN1569923A (en) * 2003-07-23 2005-01-26 上海塑杰科技有限公司 Polyamine guanidine salt copolymer and its uses in antibiotic polyester and polyamide materials
CN101037503A (en) * 2006-03-15 2007-09-19 上海高聚实业有限公司 Propanoic acid polyhexamethylene guanide and preparation method thereof
CN101562971A (en) * 2006-05-10 2009-10-21 S.K.药物公司 Synergistically enhanced disinfecting solutions
CN101720785A (en) * 2008-10-31 2010-06-09 中国石油化工股份有限公司 Compound antimicrobial and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1350022A (en) * 2000-10-19 2002-05-22 上海塑杰科技有限公司 Polyamine-guanidine salt polymer and its prepn
CN1445270A (en) * 2002-03-15 2003-10-01 上海塑杰科技有限公司 Functional agglomerates of polyolefin as well as its preparing method and application
CN1569923A (en) * 2003-07-23 2005-01-26 上海塑杰科技有限公司 Polyamine guanidine salt copolymer and its uses in antibiotic polyester and polyamide materials
CN101037503A (en) * 2006-03-15 2007-09-19 上海高聚实业有限公司 Propanoic acid polyhexamethylene guanide and preparation method thereof
CN101562971A (en) * 2006-05-10 2009-10-21 S.K.药物公司 Synergistically enhanced disinfecting solutions
CN101720785A (en) * 2008-10-31 2010-06-09 中国石油化工股份有限公司 Compound antimicrobial and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
YUMEI ZHANG等: "Synthesis and antimicrobial activity of polymeric guanidine and biguanidine salts", 《POLYMER》 *
刘海弟等: "醋酸洗必泰/二氧化硅杂化抗菌材料的制备及性能", 《中国粉体技术》 *
徐克勋: "《辽宁省化工产品手册》", 30 April 1988, 辽宁科学技术出版社 *
汪多仁: "《精细化工中间体》", 31 January 2008, 海洋出版社 *
辽宁省石油化学工业厅: "《辽宁化工产品大全》", 31 December 1994, 辽宁科学技术出版社 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105568676A (en) * 2015-12-22 2016-05-11 常熟市泽众家用纺织品有限公司 Pillowcase fabric
CN106674754A (en) * 2016-12-29 2017-05-17 上海普利特复合材料股份有限公司 Halogen-free flame-retardant high-heat-resistance antibacterial polypropylene composite material and preparation method thereof
CN107099031A (en) * 2017-04-21 2017-08-29 石家庄学院 A kind of heat resist modification polyhexamethylene guanide and its production and use
CN108048169A (en) * 2017-12-18 2018-05-18 徐润宝 A kind of wear-resistant antioxygen engine lubricating oil
CN108486680A (en) * 2018-01-30 2018-09-04 宁波三邦超细纤维有限公司 Compound imitative ice silk fiber of colored polyester-nylon and preparation method thereof
CN109303050A (en) * 2018-07-26 2019-02-05 合肥华盖生物科技有限公司 A kind of high temperature resistant type complex antimicrobials and preparation method thereof
CN109295572A (en) * 2018-10-16 2019-02-01 宜城市天舒纺织有限公司 A kind of antibacterial Quality Pure Cotton Yarn Production production technology

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